Titanium oxide (TiO 2) is one of the promising anode materials for sodium-ion batteries (SIBs) owing to its high theoretical capacity (335 mA h g−1), reasonable operation voltage (0.7 V), low cost, and low toxicity, but suffers from its low electronic conductivity and ionic diffusion coefficient. Here, the novel mesoporous hollow TiO 2-x /C nanofibers were designed and synthesized by the simple coaxial electrospinning with the annealing treatment in H 2 /Ar atmosphere (H–TiO 2-x /C). Benefitting from the oxygen vacancies (OVs), mesoporous hollow nanofibers, and conductive carbon framework, the electronic conductivity and ionic diffusion coefficient of H–TiO 2-x /C are remarkably enhanced. The as-synthesized H–TiO 2-x /C demonstrates an excellent reversible capacity of 262.4 mA h g−1 at 33.5 mA g−1, superior rate performance of 142.6 mA h g−1 at 1.675 A g−1, and prominent capacity retention of almost 100% with a capacity of 131.3 mA h g−1 over 7000 cycles under a current density of 3.35 A g−1. Moreover, the in-situ X-ray diffraction analysis and density functional theory calculation reveal that the H–TiO 2-x /C possesses stable structure and low energy barriers. Furthermore, Na-ion full-cell of Na 0.67 Ni 0.33 Mn 0.37 Ti 0.3 O 2 //H–TiO 2-x /C delivers an energy density of 398.2 Wh kg−1 with a retention of 95.1% after 100 cycles at 0.335 A g−1. This work indicates the great promise of the novel mesoporous hollow H–TiO 2-x /C nanofibers as high-performance anode materials for SIBs. [Display omitted] • The mesoporous hollow H–TiO 2-x /C nanofibers with multi-function are synthesized. • H–TiO 2-x /C delivers ultrahigh cyclic stability at a current density of 3.35 A g−1. • The structural evolution and storage mechanism is investigated for H–TiO 2-x /C. [ABSTRACT FROM AUTHOR]